Heterojunction photovoltaic device and fabrication method

ABSTRACT

A photovoltaic device and method include a doped germanium-containing substrate, an emitter contact coupled to the substrate on a first side and a back contact coupled to the substrate on a side opposite the first side. The emitter includes at least one doped layer of an opposite conductivity type as that of the substrate and the back contact includes at least one doped layer of the same conductivity type as that of the substrate. The at least one doped layer of the emitter contact or the at least one doped layer of the back contact is in direct contact with the substrate, and the at least one doped layer of the emitter contact or the back contact includes an n-type material having an electron affinity smaller than that of the substrate, or a p-type material having a hole affinity larger than that of the substrate.

RELATED APPLICATION DATA

This application is a Continuation application of co-pending U.S. patentapplication Ser. No. 13/194,301 filed on Jul. 29, 2011, incorporatedherein by reference in its entirety.

BACKGROUND Technical Field

The present invention relates to photovoltaic devices, and moreparticularly to heterojunction photovoltaic devices fabricated using alow temperature process.

Description of the Related Art

Ge solar cells are used as the bottom cells in high-efficiencymulti-junction solar cells. Since Ge is an expensive material, it isdesired to fabricate solar cells on thin layers of Ge transferred from aboule or wafer, onto a handle substrate. The electrical junctions inconventional crystalline Ge solar cells are formed by high temperatureprocesses such as diffusion, which are not compatible with typicallow-cost handle substrates such as plastic. Therefore, low temperatureprocesses are highly desired for post-processing of thin Ge waferstransferred onto low-cost handle substrates. In addition, lowering theprocess temperature may reduce the fabrication cost of the solar cellregardless of the usage of a handle substrate, as well as allowing theusage of low cost Ge wafers which may be degraded at high processtemperatures.

Referring to FIG. 1, the structure of the most high-efficiencystand-alone solar cells includes an n+ emitter c-Ge contact 10 formed byphosphorous diffusion from a spin-on-dopant at ˜600° C. and a p+ c-Geback-surface-field contact 12 is formed by screen printing or depositionof Al, followed by annealing at temperatures above the Ge—Al alloyeutectic temperature (˜425° C.). The emitter contact 10, a substratelayer 14 and the back-surface-field contact 12 all include crystallineGe (c-Ge). An emitter passivation layer 16 may be provided by a plasmaenhanced chemical vapor deposition (PECVD) of hydrogenated amorphous Si(a-Si:H). The passivation layer 16 improves the solar cell efficiency byreducing the recombination of electron-hole pairs at the surface of theemitter layer (n⁺ c-Ge). However, the passivation layer 16 is notfundamental to the device operation and may be omitted. The front(emitter) contact 10 includes the passivation layer 16 with metalfingers 20 formed through the layer 16 by lithography or by diffusion ofmetal through this passivation layer 16 at about 200° C. The backcontact 12 includes an Al layer 18. The best open-circuit voltageachieved for these cells is ˜270 mV. The low open circuit voltage is dueto (i) the low bandgap of Ge, and (ii) the lack of sufficient surfacepassivation at the front and back of the cell.

SUMMARY

A photovoltaic device includes a doped germanium-containing substrate,an emitter contact coupled to the substrate on a first side and a backcontact coupled to the substrate on a side opposite the first side. Theemitter includes at least one doped layer of an opposite conductivitytype as that of the substrate and the back contact includes at least onedoped layer of the same conductivity type as that of the substrate. Theat least one doped layer of the emitter contact or the at least onedoped layer of the back contact is in direct contact with the substrate,and the at least one doped layer of the emitter contact or the backcontact includes an n-type material having an electron affinity smallerthan that of the substrate, or a p-type material having a hole affinitylarger than that of the substrate.

A multi-junction photovoltaic device includes a top cell including aphotovoltaic cell configured to initially receive light and a bottomcell. The bottom cell includes a germanium-containing substrate coupledto an emitter contact on a front side of the substrate and a backcontact on a back side of the substrate. At least one doped layer in theemitter contact or the back contact comprised of an n-type material hasan electron affinity smaller than that of the germanium-containingsubstrate, or a p-type material having a hole affinity larger than thatof the germanium containing substrate. A passivation layer is in contactwith the at least one doped layer and disposed between the substrate andthe one of the emitter contact and the back contact.

A multi-junction photovoltaic device includes a top cell including aphotovoltaic cell configured to initially receive light and a bottomcell. The bottom cell includes a doped germanium-containing substrate,an emitter contact coupled to the substrate on a first side and a backcontact coupled to the substrate on a side opposite the first side. Theemitter includes at least one doped layer of an opposite conductivitytype as that of the substrate, and the back contact includes at leastone doped layer of the same conductivity type as that of the substrate.The at least one doped layer of the emitter contact or the at least onedoped layer of the back contact is in direct contact with the substrate,and the at least one doped layer of the emitter contact or the backcontact includes an n-type material having an electron affinity smallerthan that of the substrate, or a p-type material having a hole affinitylarger than that of the substrate.

A method for fabricating a photovoltaic device includes forming anemitter contact on a front side of a germanium-containing substrate anda back contact on a back side of the germanium substrate wherein thestep of forming includes: configuring at least one of the emittercontact and the back contact to include a doped layer in direct contactwith the germanium-containing substrate, the doped layer including oneof an n-type semiconductor material having an electron affinity smallerthan that of the germanium-containing substrate, or a p-typesemiconductor material having a hole affinity larger than that of thegermanium containing substrate; and forming a passivation layer incontact with the doped layer.

These and other features and advantages will become apparent from thefollowing detailed description of illustrative embodiments thereof,which is to be read in connection with the accompanying drawings.

BRIEF DESCRIPTION OF DRAWINGS

The disclosure will provide details in the following description ofpreferred embodiments with reference to the following figures wherein:

FIG. 1 is a cross-sectional view of a conventional c-Ge stand-alonesolar cell;

FIG. 2A is a cross-sectional view of a Ge cell with an n-type substratein accordance with the present principles;

FIG. 2B is an energy band diagram of the cell of FIG. 2A;

FIG. 3A is a cross-sectional view of a Ge cell with a p-type substratein accordance with the present principles;

FIG. 3B is an energy band diagram of the cell of FIG. 3A;

FIG. 4 is cross-sectional view of a hybrid Ge cell with an n-typesubstrate having one contact in accordance with the present principlesand the other contact being a conventional contact;

FIG. 5 is cross-sectional view of a hybrid Ge cell with a p-typesubstrate having one contact in accordance with the present principlesand the other contact being a conventional contact;

FIG. 6 is a cross-sectional view of a multi-junction device having a Gebottom cell with an n-type substrate in accordance with the presentprinciples and a top cell including III-V materials in accordance withone embodiment;

FIG. 7 is a cross-sectional view of a multi-junction device having a Gebottom cell with a p-type substrate in accordance with the presentprinciples and a top cell including III-V materials in accordance withone embodiment;

FIG. 8 is a cross-sectional view of a multi-junction device having a Gebottom cell with an n-type substrate in accordance with the presentprinciples and a top cell including a p-i-n stack in accordance with oneembodiment;

FIG. 9 is a cross-sectional view of a multi-junction device having a Gebottom cell with an n-type substrate in accordance with the presentprinciples and a top cell including multiple p-i-n stacks with differentbase materials in accordance with one embodiment;

FIG. 10 is a cross-sectional view of a multi-junction device having a Gebottom cell with a p-type substrate in accordance with the presentprinciples and a top cell including CdS/CdTe, CdS/CIGS, CdS/CZTS orCdS/CZTSe in accordance with one embodiment;

FIG. 11 is a block/flow diagram showing an illustrative method forfabricating photovoltaic devices in accordance with one illustrativeembodiment;

FIG. 12A is a cross-sectional view of a control device fabricated forcomparison with a test device in FIG. 12B;

FIG. 12B is a cross-sectional view of a test device in accordance withthe present principles; and

FIG. 13 is a plot of the test device (FIG. 12B) versus the controldevice (FIG. 12A) showing improved performance in accordance with thepresent principles.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

In accordance with the present principles, device structures andfabrication methods are provided for improving open circuit voltage of aphotovoltaic cell by using wider-bandgap contacts with proper bandgapengineering to avoid compromising fill-factor of the cell. In addition,a fabrication method is provided to reduce process temperatures to aslow as ˜200° C. The low process temperature (i) reduces the thermalbudget and therefore potentially lowers process cost, (ii) preserves thebulk-lifetime of the absorption layer of the device, and (iii) issuitable for low-temperature low-cost flexible substrates (this isparticularly useful if the substrate includes a thin layer ofcrystalline germanium (c-Ge) or other crystalline form transferred ontoa handle substrate, such as plastic.

It is to be understood that the present invention will be described interms of a given illustrative architecture having substrates andphotovoltaic stacks; however, other architectures, structures,substrates, materials and process features and steps may be variedwithin the scope of the present invention.

It will also be understood that when an element such as a layer, regionor substrate is referred to as being “on” or “over” another element, itcan be directly on the other element or intervening elements may also bepresent. In contrast, when an element is referred to as being “directlyon” or “directly over” another element, there are no interveningelements present. It will also be understood that when an element isreferred to as being “connected” or “coupled” to another element, it canbe directly connected or coupled to the other element or interveningelements may be present. In contrast, when an element is referred to asbeing “directly connected” or “directly coupled” to another element,there are no intervening elements present.

A design for a photovoltaic device may be created for integrated circuitintegration or may be combined with components on a printed circuitboard. The circuit /board may be embodied in a graphical computerprogramming language, and stored in a computer storage medium (such as adisk, tape, physical hard drive, or virtual hard drive such as in astorage access network). If the designer does not fabricate chips or thephotolithographic masks used to fabricate chips or photovoltaic devices,the designer may transmit the resulting design by physical means (e.g.,by providing a copy of the storage medium storing the design) orelectronically (e.g., through the Internet) to such entities, directlyor indirectly. The stored design is then converted into the appropriateformat (e.g., GDSII) for the fabrication of photolithographic masks,which typically include multiple copies of the chip design in questionthat are to be formed on a wafer. The photolithographic masks areutilized to define areas of the wafer (and/or the layers thereon) to beetched or otherwise processed.

Methods as described herein may be used in the fabrication ofphotovoltaic devices and/or integrated circuit chips with photovoltaicdevices. The resulting devices/chips can be distributed by thefabricator in raw wafer form (that is, as a single wafer that hasmultiple unpackaged devices/chips), as a bare die, or in a packagedform. In the latter case the device/chip is mounted in a single chippackage (such as a plastic carrier, with leads that are affixed to amotherboard or other higher level carrier) or in a multichip package(such as a ceramic carrier that has either or both surfaceinterconnections or buried interconnections). In any case thedevices/chips is then integrated with other chips, discrete circuitelements, and/or other signal processing devices as part of either (a)an intermediate product, such as a motherboard, or (b) an end product.The end product can be any product that includes integrated circuitchips, ranging from toys, energy collectors, solar devices and otherapplications including computer products or devices having a display, akeyboard or other input device, and a central processor.

It should be noted that the drawings with include listings of compoundsand forms or the compounds which are for illustrative purposes and easeof understanding and should not be construed as limiting. For example, asubstrate may include the layer c-Ge; however, other forms of germanium(polycrystalline, nano/microcrystalline and single crystalline) may alsobe employed. Notations such as SiGe or SiC include any ratio of thesecompounds such as Si_(1-x)Ge_(x) or Si_(1-y)C_(y). These compounds maytake different forms as well, e.g., polycrystalline,nano/microcrystalline, single crystalline or even amorphous.

Referring now to the drawings in which like numerals represent the sameor similar elements and initially to FIGS. 2A and 2B, a structure of aphotovoltaic device 100 (FIG. 2A) and its corresponding energy banddiagram (FIG. 2B) are illustratively shown. The cell 100 includes asubstrate 102. The substrate 102 may include a germanium-containingsubstrate 102, such as an n-type crystalline germanium (c-Ge). Examplesof the germanium containing substrates may include but are not limitedto crystalline, poly-crystalline or multi-crystalline germanium, andcrystalline, poly-crystalline or multi-crystalline silicon-germanium. Ap⁺ type layer 104 which may include Si_(1-x1)Ge_(x1) and may besingle-crystalline or poly/micro-crystalline, is grown using one of thefollowing methods: (i) plasma enhanced chemical vapor deposition (PECVD)or hot-wire chemical vapor deposition (HWCVD) growth from a mixture ofsilane, germane (for x1>0), hydrogen and diborane at conditions leadingto single-crystalline growth at deposition temperatures as low as 200°C.; (ii) PECVD or HWCVD of p⁺ amorphous hydrogenated silicon germanium(a-Si_(x1)Ge_(1-x1):H) from the same gas mixture at known conditionsleading to amorphous film growth at ˜200° C. or below, orsputtering/co-sputtering or thermal/e-beam evaporation/co-evaporation toform known solid sources, followed by solid-phase crystallization of thelayer using high-temperature annealing (e.g., up to ˜600° C.); or (iii)chemical vapor deposition (CVD) or molecular beam epitaxy (MBE) growth.Examples of CVD include but are not limited to rapid thermal CVD(RTCVD), low-pressure CVD (LPCVD) and ultra-high-vacuum CVD (UHVCVD).The value of x1 may be constant or vary across the SiGe layer 104. Thep⁺ layer 104 may be passivated by a PECVD or HWCVD growth of intrinsiclayer 106 which may include a-Si_(1-x2)Ge_(x2):H from silane, germaneand hydrogen at ˜200° C. The value of x2 may be constant or vary acrossthe SiGe layer 106. There is no correlation between x1 and x2.

An intrinsic layer 110 and an n⁺ layer 108 are preferably grown by PECVDor HWCVD from silane, hydrogen, methane and/or ethylene/acetylene (fory1, y2>0), and phosphorous (for the n⁺ layer 108) at ˜200° C. The n+layer 108 may include amorphous hydrogenated silicon carbide(a-Si_(1-y1)C_(y1):H). Intrinsic layer 110 may include(a-Si_(1-y2)C_(y2):H). The SiGe layers 104 and 106 may include carbonamorphous hydrogenated silicon carbide (e.g., by flowing methane and/orethylene/acetylene during formation) and the SiC layers 108 and 110 mayinclude Ge (e.g., by flowing germane during formation). The SiGe and SiClayers 104, 106, 108 and 110 may include fluorine, nitrogen, oxygenand/or deuterium. The values of y1 and y2 may be constant or vary acrossthe SiC layers 108, 110. There is no correlation between y1 and y2, orbetween x1/x2 and y1/y2.

A thickness for the intrinsic layers (i-layers) 106 and 110 may beapproximately about 5 nm but thicknesses in the range of 0-25 nm arealso contemplated. The thickness for the n⁺ layer 108 is in the range of0-50 nm. The thickness also depends on the type of contact, e.g., arange for the emitter contact is preferably between about 3 nm to about8 nm but the thickness for the back contact is preferably between 5 nmand 20 nm.

Doping of the p⁺ layer 104 may be about ˜10¹⁹ cm⁻³ with a thickness ofabout 10 nm. Doping in the range of 10¹⁸-10²⁰ cm⁻³ and thicknesses inthe range of 1 nm-150 nm are contemplated for layer 104. A thicker p⁺layer 104 is needed for a lower doping concentration.

The structure of device 100 further includes electrodes 112. Electrodes112 include a conductor which may be a transparent conductive materialsuch as a transparent conductive oxide (TCO), such as, e.g., Al-dopedzinc oxide, indium tin oxide, etc. or a metal (such as, e.g., tungsten,silver, aluminum, etc.). If layer 112 is composed of a transparentconductive material, metal fingers 114 are needed to allow for lowelectrical contact resistance, while if layer 112 is composed of ametal, the electrical conductivity of the contact is sufficient and themetal fingers 114 are not needed. At least one of the layers 112 iscomposed of a transparent conductive material to permit light to enterand be absorbed. If both layers 112 are composed of transparentconductive materials, the light can enter from both sides of the cell100 (a bifacial cell).

FIG. 2B shows the equilibrium Fermi level denoted by E_(F), and theconduction band and valance band edges denoted by E_(c) and E_(v),respectively. Open circuit voltage of the cell 100 (V_(oc)), times thecharge of an electron (q), i.e., q×V_(oc) is equal to the separation ofthe quasi Fermi level for electrons “e” at an emitter (front) side andthe quasi Fermi level for holes “h” at a back contact under illumination(not shown). A conventional Ge cell employs crystalline Ge back andfront contacts. Replacing the conventional crystalline Ge contacts withmaterials such as a-Si:H and a-SiC:H significantly reduces the processtemperature, but it is restrictive to the flow of holes in particular.This is because the valence band offset between crystalline Ge and thesematerials is large (−0.7 eV or larger).

In accordance with the present principles, the emitter contact 120and/or the back contact 122 are configured to reduce the valence bandoffset described above by including a doped layer (e.g., 104, 108)having a composition of elements adjusted to provide a bandgap thatimproves open circuit voltage while at least maintaining fill factor(i.e. not restricting carrier flow, in particular holes). In aparticularly useful embodiment, the doped layer may includeSi_(x)Ge_(1-x) or Si_(x)C_(1-x). The value of x is adjusted duringformation or after formation of the doped layer to adjust the band gapof the doped layers to enable a reduced band offset especially at thevalence band. The value of x may be constant or vary across the SiGelayer.

The emitter contact 120 and/or the back contact 122 includes at leastone doped layer comprised of an n-type material having an electronaffinity smaller than that of the germanium-containing substrate 102, ora p-type material having a hole affinity larger than that of thegermanium containing substrate 120. A passivation layer (106, 110) isformed in contact with the doped layer and is disposed between thesubstrate and the one of the emitter contact 120 and the back contact122. The passivation layers 106 and 110 are intrinsic but may beintentionally or unintentionally doped. Intentional doping may beincorporated, for example, by flowing a dopant gas during deposition.Unintentional doping may be incorporated, for example, by the presenceof the dopant atom residues in the deposition chamber (for example, ifthe same chamber is used for depositing both intrinsic and dopedlayers). The passivation layers 106 and 110 improve the solar cellefficiency by reducing the recombination of electron-hole pairs (at thetop surface of layer 104 and bottom surface of substrate 102,respectively). However, the passivation layers are not fundamental tothe device operation and may be omitted without losing the devicefunctionality.

The structure improves the open circuit voltage of the cell 100 by usingwider-bandgap contacts (e.g., layers 104/106 and/or layers 108/110) withproper bandgap engineering to avoid compromising the fill-factor of thecell. The bandgap of contact materials, i.e., layers 104/106 and 108/110is in the range of 0.6 eV-4.0 eV, with the range of 0.7-1.8 eV beingmore preferred. The n-type contact material(s) (i.e., layers 108/110) ischosen to have a lower electron affinity than that of thegermanium-containing substrate material 102. The difference between theelectron affinities of two materials is referred to as the conductionband-offset between the two materials. Increasing the conduction bandoffset between layers 108/110 and the absorption layer 102 increases theopen circuit voltage of the cell, but an excessively large conductionband offset reduces the fill-factor of the cell by blocking the electronflow. The conduction band-offset between layers 108/110 and theabsorption layer 102 may be in the range of 0.0-1.0 eV, with the rangeof 0.05-0.5 eV being more typical. The sum of electron affinity (χ_(e))and bandgap energy (E_(g)), i.e., χ_(e)+E_(g) of a material is referredto as the hole affinity (χ_(h)) of the material. The p-type contactmaterial(s) (i.e., layers 104/106) is chosen to have a higher holeaffinity than that of the germanium-containing substrate material 102.The difference between the hole affinities of two materials is referredto as the valence band-offset between the two materials. Increasing thevalence band offset between layers 104/106 and the absorption layer 102increases the open circuit voltage of the cell, but an excessively largevalence band offset reduces the fill-factor of the cell by blocking thehole flow. The valence band-offset between layers 104/106 and theabsorption layer 102 may be in the range of 0-1.0 eV, with the range of0.05-0.5 eV being more typical.

Referring to FIGS. 3A and 3B, a structure of a photovoltaic device 200(FIG. 3A) and its corresponding energy band diagram (FIG. 3B) areillustratively shown. The cell 200 includes a substrate 103. Thesubstrate 103 may include a p-type germanium containing material, e.g.,crystalline Ge (c-Ge). The structure with a p-type substrate 103 has itscontacts reversed with respect to the cell 100. As described above, thep⁺ type layer 104 which may include Si_(1-x1)Ge_(x1) and may besingle-crystalline or poly/micro-crystalline, is grown using one of thefollowing methods: (i) plasma enhanced chemical vapor deposition (PECVD)or hot-wire chemical vapor deposition (HWCVD) growth from a mixture ofsilane, germane (for x1>0), hydrogen and diborane at conditions leadingto single-crystalline growth at deposition temperatures as low as 200°C.; (ii) PECVD or HWCVD of p⁺ amorphous hydrogenated silicon germanium(a-Si_(x1)Ge_(1-x1):H) from the same gas mixture at known conditionsleading to amorphous film growth at ˜200° C. or below, orsputtering/co-sputtering or thermal/e-beam evaporation/co-evaporationfrom known solid sources, followed by solid-phase crystallization of thelayer using high-temperature annealing (e.g., up to ˜600° C.); or (iii)chemical vapor deposition (CVD) or molecular beam epitaxy (MBE) growth.Examples of CVD include but are not limited to rapid thermal CVD(RTCVD), low-pressure CVD (LPCVD) and ultra-high-vacuum CVD (UHVCVD).The p⁺ layer 104 is passivated by a PECVD or HWCVD of intrinsic layer106 which may include a-Si_(1-x2)Ge_(x2):H from silane, germane andhydrogen at ˜200° C. The values of x1 and x2 may be constant or varyacross the SiGe layers (104, 106). There is no correlation between x1and x2.

The intrinsic layer 110 and the n⁺ layer 108 are preferably grown byPECVD or HWCVD from silane, hydrogen, methane and/or ethylene/acetylene(for x1, x2>0), and phosphorous (for the n⁺ layer 108) at ˜200° C. Then+ layer 108 may include amorphous hydrogenated silicon carbide(a-Si_(1-y1)C_(y1):H). Intrinsic layer 110 may include(a-Si_(1-y2)C_(y2):H). The SiGe layers 104 and 106 may include carbon(e.g., by flowing methane and/or ethylene/acetylene during formation)and the SiC layers 108 and 110 may include Ge (e.g., by flowing germaneduring formation). The SiGe and SiC layers 104, 106, 108 and 110 maininclude fluorine, nitrogen, oxygen and/or deuterium. The values of y1and y2 may be constant or vary across the SiC layers. There is nocorrelation between y1 and y2, or between x1/x2 and y1/y2.

As before, thickness for the intrinsic layers (i-layers) 106 and 110 maybe approximately about 5 nm but thicknesses in the range of 0-25 nm arealso contemplated. The thickness for the n⁺ layer 108 is in the range of0-50 nm. The thickness also depends on the type of contact, e.g., arange for the emitter contact is preferably between about 3 nm to about8 nm but the thickness for the back contact is preferably between 5 nmand 20 nm.

Doping of the p⁺ layer 104 may be about ˜10¹⁹ cm⁻³ with a thickness ofabout 10 nm. Doping in the range of 10¹⁸-10²⁰ cm⁻³ and thicknesses inthe range of 1 nm-150 nm are contemplated for layer 104. A thicker p⁺layer 104 is needed for a lower doping concentration.

The cell 200 further includes electrodes 112. Electrodes 112 include aconductor which may be a transparent conductive material such as atransparent conductive oxide (TCO), such as, e.g., Al-doped zinc oxide,indium tin oxide, etc. or a metal (such as, e.g., tungsten, silver,aluminum, etc.). If layer 112 is composed of a transparent conductivematerial, metal fingers 114 are needed to allow for low electricalcontact resistance, while if layer 112 is composed of a metal, theelectrical conductivity of the contact is sufficient and the metalfingers 114 are not needed. At least one of the layers 112 is composedof a transparent conductive material to permit light to enter and beabsorbed. If both layers 112 are composed of transparent conductivematerials, the light can enter from both sides of the cell 200 (abifacial cell).

FIG. 3B shows the equilibrium Fermi level (E_(F)) and the conductionband and valance band edges (E_(c) and E_(v), respectively). Opencircuit voltage of the cell 200 (Voc), times the charge of an electron(q), i.e., q×V_(oc) is equal to the separation of the quasi Fermi levelfor electrons “e” at an emitter (front) side and the quasi Fermi levelfor holes “h” at a back contact under illumination (not shown).

The structure improves the open circuit voltage of the cell 200 by usingwider-bandgap contacts (e.g., layers 104/106 and/or layers 108/110) withproper bandgap engineering to avoid compromising the fill-factor of thecell. The bandgap of contact materials, i.e. layers 104/106 and 108/110is in the range of 0.6-4.0 eV, with the range of 0.7-1.8 eV being morepreferably. The n-type contact material(s) (i.e., layers 108/110) ischosen to have a lower electron affinity than that of thegermanium-containing substrate material 103. Increasing the conductionband offset between layers 108/110 and the absorption layer 103increases the open circuit voltage of the cell, but an excessively largeconduction band offset reduces the fill-factor of the cell by blockingthe electron flow. The conduction band-offset between layers 108/110 andthe absorption layer 103 may be in the range of 0.0-1.0 eV, with therange of 0.05-0.5 eV being more typical. The p-type contact material(s)(i.e. layers 104/106) is chosen to have a higher hole affinity than thatof the germanium-containing substrate material 103. Increasing thevalence band offset between layers 104/106 and the absorption layer 103increases the open circuit voltage of the cell but an excessively largevalence band offset reduces the fill-factor of the cell by blocking thehole flow. The valence band-offset between layers 104/106 and theabsorption layer 103 may be in the range of 0.0-1.0 eV, with the rangeof 0.05-0.5 eV being more typical.

Referring to FIGS. 4 and 5, examples of hybrid cells 300 and 400 arerespectively shown in accordance with other illustrative embodiments.The hybrid structures 300 and 400 include a contact in accordance withthe present principles and a contact on one side of the cell which has aconventional structure.

In the example shown in FIG. 4, the cell 300 includes an n-type c-Gesubstrate 306 and a top contact 304, which includes a p+ doped layer 308including, e.g., c-Si_(1-x1)Ge_(x1):H and an intrinsic layer 310including, e.g., a-Si_(1-x2)Ge_(x2):H. A bottom contact 302 may includeany known contact structure and includes an n+ c-Ge layer 316 and ametal contact 318 (e.g., Aluminum) in this example. Other structures orlayers may include an electrode 112, metal fingers 314, etc. The valuesof x1 and x2 may be constant or vary across the SiGe layers. There is nocorrelation between x1 and x2.

In the example shown in FIG. 5, the cell 400 includes a p-type c-Gesubstrate 406 and a top contact 404, which includes an n+ doped layer408 including, e.g., a-Si_(1-y1)C_(y1):H and an intrinsic layer 410including, e.g., a-Si_(1-y2)C_(y2):H. A bottom contact 402 may includeany known contact structure and includes a p+ c-Ge layer 416 and a metalcontact 418 (e.g., Aluminum) in this example. Other structures or layersmay include an electrode 112, metal fingers 414, etc. The values of y1and y2 may be constant or vary across the SiC layer. There is nocorrelation between y1 and y2.

Referring to FIG. 6, a multi-junction embodiment includes a bottom cell504 formed in accordance with the present principles and a top cell 502having one or more conventional cells. The bottom cell 504 employs ann-type c-Ge substrate 506, an n+doped layer 508 including, e.g.,a-Si_(1-y1)C_(y1):H and an intrinsic layer 510 including, e.g.,a-Si_(1-y2)C_(y2):H. The values of y1 and y2 may be constant or varyacross the SiC layer. There is no correlation between y1 and y2. The topcell 502 may include any known contact structure and may include III-Vmaterials or the like. Other structures or layers may include ananti-reflection coating (ARC) 512, electrodes 112, metal fingers 514,etc.

Referring to FIG. 7, another multi-junction embodiment includes a bottomcell 604 formed in accordance with the present principles and a top cell502 having one or more conventional cells. The bottom cell 604 employs ap-type c-Ge substrate 606, a p+ doped layer 608 including, e.g.,a-Si_(1-x1)Ge_(x1):H and an intrinsic layer 610 including, e.g.,a-Si_(1-x2)Ge_(x2):H. The values of x1 and x2 may be constant or varyacross the SiGe layers. There is no correlation between x1 and x2. Thetop cell 502 may include any known contact structure and may includeIII-V materials or the like. Other structures or layers may include ananti-reflection coating (ARC) 512, electrodes 112, metal fingers 514,etc.

Referring to FIG. 8, another multi-junction embodiment includes a bottomcell 704 formed in accordance with the present principles, a top cell702 having one or more conventional cells and a tunnel layer 703disposed therebetween. The bottom cell 704 employs an n-type c-Gesubstrate 706, an n+ doped layer 708 including, e.g.,a-Si_(1-y1)C_(y1):H and an intrinsic layer 710 including, e.g.,a-Si_(1-y2)C_(y2):H. The values of y1 and y2 may be constant or varyacross the SiC layer. There is no correlation between y1 and y2. Thebottom cell 704 employs a p+ doped layer 716 including, e.g.,c-Si_(1-x1)Ge_(x1):H and an intrinsic layer 718 including, e.g.,a-Si_(1-x2)Ge_(x2):H. The top cell 702 may include a p-i-n a-Si:H cellor cells with a p+-doped a-Si:H layer 724, an a-Si:H intrinsic layer 722and an n+-type doped a-Si:H layer 720. The values of x1 and x2 may beconstant or vary across the SiGe layers. There is no correlation betweenx1 and x2. There is also no correlation between x1/x2 and y1/y2. Otherstructures or layers may include a metal grid 714, TCO layer 726,electrode 112, metal fingers 514, etc.

Referring to FIG. 9, another multi-junction embodiment includes thebottom cell 704 formed in accordance with the present principles and topcells 806, 808, 810 including conventional p-i-n structures withtunneling layers 803 disposed therebetween. The bottom cell 704 isdescribed with respect to FIG. 8. The top cells 806, 808 and 810 includep+-i-n+ layers with different base materials. For example, the pin stackfor layer 806 includes microcrystalline Si:H (this means the n-typelayer, the intrinsic layer and the p-type layer all include the samebase material). The pin stack for layer 808 includes amorphous SiGe:H,and the pin stack for layer 810 includes amorphous Si:H. Otherstructures and materials are also contemplated. Other structures orlayers may include a metal grid 714, TCO layer 726, etc.

Referring to FIG. 10, another multi-junction embodiment includes abottom cell 904 formed in accordance with the present principles and atop cell 902 formed from conventional CdS/CdTe, CdS/CIGS (copper indiumgallium selenide), CdS/CZTS (copper zinc tin sulfide), CdS/CZTSe (copperzinc tin selenide) or other cells with an optional tunneling layer 903disposed therebetween. In this illustrative embodiment, the bottom cell904 includes the structure described with respect to FIG. 3A. In thisexample, the top cell 902 includes a p-doped CdTe, CIGS, CZTS or CZTSeintrinsic layer 910, an n+-doped CdS layer 908 and a p+ doped region orbuffer layer 912.

The device structures described in FIGS. 6 through 10 improve the opencircuit voltage of the multi-junction cell (which is the sum of the opencircuit voltages of the single-junction cells present in themulti-junction cell) by employing the disclosed germanium-containingbottom cell which has an improved open circuit voltage compared toconventional cells without compromising the fill factor of the bottomcell (and therefore the fill-factor of the multi-junction cell).

Referring to FIG. 11, an illustrative method for fabricatingphotovoltaic devices in accordance with the present principles isillustratively shown. It should also be noted that, in some alternativeimplementations, the functions noted in the block may occur out of theorder noted in FIG. 11. For example, two blocks shown in succession may,in fact, be executed substantially concurrently, or the blocks maysometimes be executed in the reverse order, depending upon thefunctionality involved.

In block 1002, an emitter contact is formed on a front side of agermanium-containing substrate, and a back contact is formed on a backside of the germanium-containing substrate. One of the contacts may beformed on the substrate first and then the other contact is formed onthe substrate. The formation of the contacts preferably includes lowtemperature processes. In block 1004, at least one of the emittercontact and the back contact are configured by including a compositionof elements adjusted, as disclosed herein, to improve open circuitvoltage of the solar cell while at least maintaining fill factor. Thedoped layer includes, e.g., one of Si_(1-y)C_(y) and Si_(1-x)Ge_(x)

In block 1006, a passivation layer may be formed in contact with thedoped layer and disposed between the substrate and the one of theemitter contact and the back contact. The passivation layer may beformed by using plasma enhanced chemical vapor deposition (PECVD) orhot-wire chemical vapor deposition (HWCVD) at conditions leading toamorphous film growth at a temperature of less than about 200° C. toabout 400° C., lower temperatures being preferred.

In block 1008, adjustments may be made to the doped layer during itsformation or after its formation by changing the composition ratios(e.g., x or y values). The formation of the contacts (emitter or back)is preferably performed using low temperature deposition processes. Anemitter contact includes at least one doped layer of the oppositeconductivity type as that of the substrate on a front side of thesubstrate and a back contact includes an intrinsic and/or doped layer(s)of the same conductivity type as that of the substrate, and/orconductive layer(s) such as metal on a back side of the substrate. Theat least one doped layer in the emitter contact or the back contactincludes an n-type material having an electron affinity smaller thanthat of the germanium-containing substrate, and/or a p-type materialhaving a hole affinity larger than that of the germanium containingsubstrate.

In block 1012, a plasma enhanced chemical vapor deposition (PECVD), orhot-wire chemical vapor deposition (HWCVD) may be employed at conditionsleading to single-crystalline growth at deposition temperatures at about200° C. (e.g., less than 200° C. to about 400° C.). In block 1014, aplasma enhanced chemical vapor deposition (PECVD), hot-wire chemicalvapor deposition (HWCVD), sputtering, or thermal/e-beam evaporation, atconditions leading to amorphous film growth at a temperature of about200° C. (e.g., less than 200° C. to about 400° C.) and a solid-phasecrystallization of the doped layer employing annealing. The annealingmay be performed at a high temperature (e.g., up to about 650° C.) or alonger term low-temperature anneal. In block 1016, forming the dopedlayer may include depositing the doped layer with chemical vapordeposition (CVD) or molecular beam epitaxy (MBE). Examples of CVDinclude but are not limited to rapid thermal CVD, low-pressure CVD andultra-high-vacuum CVD.

In block 1020, at least one other photovoltaic device is formed toprovide a multi-junction photovoltaic device. The at least one otherphotovoltaic device may include a cell having one or more of a III-Vmaterial cell, a p-i-n stack, multiple p-i-n stacks, a CdS/CdTe cell,CdS/CIGS (copper indium gallium selenide) cell, a CdS/CZTS (copper zinctin sulfide) cell, and a CdS/CZTSe (copper zinc tin selenide) cell. Inblock 1022, processing continues to complete the device or devices.

Referring to FIGS. 12A and 12B, a photovoltaic test device 1100 wasfabricated in accordance with the structure and one of the methods inaccordance with the present principles (FIG. 12B) and compared to acontrol sample 1050 (FIG. 12A). The photovoltaic device 1100 wasfabricated using PECVD growth of a p⁺ a-Si:H layer at ˜200° C., followedby rapid thermal annealing at ˜600° C. for solid-phase crystallizationof p⁺ a-Si:H to form p⁺ poly-Si 1102. The thickness of the p⁺ a-Si:H(and therefore the p⁺ poly-Si layer 1102) is less than 15 nm. Anoptional passivation layer was not grown on the p⁺ poly-Si layer 1102.An emitter structure typically used for Si heterojunction solar cellscomprised of a p⁺/i a-Si:H stack 1052 was deposited by PECVD on thecontrol sample 1050 at ˜200° C. The thickness of the p⁺/i a-Si:H stack1052 is less than 15 nm. A PECVD stack 1054 comprised of n⁺/i a-Si:H wasdeposited on the back side of both devices at ˜200° C., followed by thesputtering of a TCO 1058 and evaporation of the metal fingers 1056 andthe back contact metal on both devices. The thickness of the n⁺/i a-Si:Hstack 1054 is less than 30 nm. The experimental output characteristicsof the two devices under an illumination intensity of one sun is plottedin FIG. 13. The control device 1050 has a low short circuit currentdensity of ˜5 mA/cm² and a fill-factor of less than 20%, while the testdevice 1100 shows a significantly higher short circuit current densityof ˜50 mA/cm² and a fill-factor of over 40%. This is primarily becausethe valence band offset between a-Si:H 1052 and c-Ge 1060 (approximately0.7-0.9 eV) is reduced by solid-phase crystallization of a-Si:H intopoly-Si 1102 (approximately 0.3-0.5 eV) allowing for improved carriertransport at the emitter junction.

Having described preferred embodiments for heterojunction devices andmethods for fabrication (which are intended to be illustrative and notlimiting), it is noted that modifications and variations can be made bypersons skilled in the art in light of the above teachings. It istherefore to be understood that changes may be made in the particularembodiments disclosed which are within the scope of the invention asoutlined by the appended claims. Having thus described aspects of theinvention, with the details and particularity required by the patentlaws, what is claimed and desired protected by Letters Patent is setforth in the appended claims.

What is claimed is:
 1. A multi-junction photovoltaic device comprising:a top cell including a photovoltaic cell configured to initially receivelight; a bottom cell comprising: a germanium-containing substratecoupled to an emitter contact on a front side of the substrate and aback contact on a back side of the substrate; at least one doped layerin the emitter contact or the back contact comprised of an n-typematerial having an electron affinity smaller than that of thegermanium-containing substrate, or a p-type material having a holeaffinity larger than that of the germanium containing substrate; and apassivation layer in contact with the at least one doped layer anddisposed between the substrate and the one of the emitter contact andthe back contact.
 2. The device as recited in claim 1, wherein the atleast one doped layer of the emitter contact or the back contactincludes one of SiC and SiGe.
 3. The device as recited in claim 1,wherein the at least one doped layer of the emitter contact or the backcontact includes crystalline SiGe and a passivation layer is formed incontact with the at least one doped layer and the substrate, thepassivation layer including amorphous SiGe.
 4. The device as recited inclaim 1, wherein the at least one doped layer of the emitter contact orthe back contact includes amorphous SiC and a passivation layer isformed in contact with the at least one doped layer, the passivationlayer including amorphous SiC.
 5. The device as recited in claim 1,wherein the substrate includes n-type crystalline Ge or n-typecrystalline SiGe; the emitter contact includes a SiGe doped layer and anamorphous SiGe passivation layer; and the back contact includes anamorphous SiC doped layer and an amorphous SiC passivation layer.
 6. Thedevice as recited in claim 1, wherein the substrate includes p-typecrystalline Ge or p-type crystalline SiGe; the emitter contact includesan amorphous SiC doped layer and an amorphous SiC passivation layer; andthe back contact includes a SiGe doped layer and an amorphous SiGepassivation layer.
 7. The device as recited in claim 1, furthercomprising a passivation layer in contact with the at least one dopedlayer of the emitter contact and the back contact.
 8. The device asrecited in claim 1, wherein the at least one doped layer of the backcontact includes at least one of an intrinsic layer, a doped layer and aconductive layer.
 9. The device as recited in claim 1, wherein the topcell includes a cell having one or more of a III-V material cell, ap-i-n stack, multiple p-i-n stacks, a CdS/CdTe cell, CdS/CIGS (copperindium gallium selenide) cell, a CdS/CZTS (copper zinc tin sulfide)cell, and a CdS/CZTSe (copper zinc tin selenide) cell.
 10. Amulti-junction photovoltaic device comprising: a top cell including aphotovoltaic cell configured to initially receive light; a bottom cellcomprising: a doped germanium-containing substrate; an emitter contactcoupled to the substrate on a first side; and a back contact coupled tothe substrate on a side opposite the first side; the emitter includingat least one doped layer of an opposite conductivity type as that of thesubstrate and the back contact including at least one doped layer of thesame conductivity type as that of the substrate; wherein the at leastone doped layer of the emitter contact or the at least one doped layerof the back contact is in direct contact with the substrate and the atleast one doped layer of the emitter contact or the back contactincludes an n-type material having an electron affinity smaller thanthat of the substrate, or a p-type material having a hole affinitylarger than that of the substrate.
 11. The device as recited in claim10, wherein the at least one doped layer of the emitter contact or theback contact includes one of SiC and SiGe.
 12. The device as recited inclaim 10, wherein the at least one doped layer of the emitter contact orthe back contact includes crystalline SiGe and a passivation layer isformed in contact with the at least one doped layer and the substrate,the passivation layer including amorphous SiGe.
 13. The device asrecited in claim 10, wherein the at least one doped layer of the emittercontact or the back contact includes amorphous SiC and a passivationlayer is formed in contact with the at least one doped layer, thepassivation layer including amorphous SiC.
 14. The device as recited inclaim 10, wherein the substrate includes n-type crystalline Ge or n-typecrystalline SiGe; the emitter contact includes a SiGe doped layer and anamorphous SiGe passivation layer; and the back contact includes anamorphous SiC doped layer and an amorphous SiC passivation layer. 15.The device as recited in claim 10, wherein the substrate includes p-typecrystalline Ge or p-type crystalline SiGe; the emitter contact includesan amorphous SiC doped layer and an amorphous SiC passivation layer; andthe back contact includes a SiGe doped layer and an amorphous SiGepassivation layer.
 16. The device as recited in claim 10, furthercomprising a passivation layer in contact with the at least one dopedlayer of the emitter contact and the back contact.
 17. The device asrecited in claim 10, wherein the at least one doped layer of the backcontact includes at least one of an intrinsic layer, a doped layer and aconductive layer.
 18. The device as recited in claim 10, wherein the topcell includes a cell having one or more of a III-V material cell, ap-i-n stack, multiple p-i-n stacks, a CdS/CdTe cell, CdS/CIGS (copperindium gallium selenide) cell, a CdS/CZTS (copper zinc tin sulfide)cell, and a CdS/CZTSe (copper zinc tin selenide) cell.